Bicyclo[2.2.1] heptane derivative

ABSTRACT

A bicyclo[2.2.1]heptane derivative represented by following general formula (1): 
                         
wherein R 1  and R 2  each represent hydrogen atom or methyl group, and R 3  represents methyl group or ethyl group. The derivative is suitable as a high viscosity hydrocarbon base material used for tackfiers for adhesives and process oils for rubber and resins.

TECHNICAL FIELD

The present invention relates to a bicyclo[2.2.1]heptane derivative and,more particularly, to a bicyclo[2.2.1]heptane derivative suitable as ahigh viscosity hydrocarbon base material used for tackfiers foradhesives and process oils for rubber and resins.

BACKGROUND ART

High viscosity hydrocarbon base materials are used for tackfiers foradhesives and process oils for rubber and resins. As the high viscosityhydrocarbon base material, polybutene, ethylene-propylene oligomers andpoly-α-olefins have heretofore been used. However, the above basematerials have a drawback in that materials which can be used incombination are restricted due to poor compatibility with variousorganic substances.

When workability in mixing is considered, it is preferable thatviscosity is small during mixing so that the mixing is facilitated.Therefore, it is preferable that the base material has aviscosity-temperature characteristic such that viscosity is low at hightemperatures (during the mixing) and high at temperatures around theroom temperature (during the use). In other words, a small viscosityindex is preferable. The conventional base materials described abovehave a drawback in that the viscosity index is 100 or greater and thechange in viscosity with temperature is small.

The present invention has been made to overcome the above drawbacks andhas an object of providing a compound exhibiting excellent compatibilitywith various organic substances and has a small viscosity index.

DISCLOSURE OF THE INVENTION

As the result of intensive studies by the present inventors, it wasfound that specific bicyclo[2.2.1]heptane derivatives exhibit thedesirable properties described above as the object of the presentinvention. The present invention has been completed based on thisknowledge.

The present invention provides:

-   1. A bicyclo[2.2.1]heptane derivative represented by following    general formula (1):

-    wherein R¹ and R² each represent hydrogen atom or methyl group, and    R³ represents methyl group or ethyl group; and-   2. A bicyclo[2.2.1]heptane derivative according to Claim 1, which is    3-methyl-2-[(3-methylbicyclo[2.2.1]hept-2-yl)methyl]-2-[(2,3-dimethylbicyclo[2.2.1]-hept-2-yl)methyl]bicyclo[2.2.1]heptane.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a mass chromatogram of a hydrogenation product of a trimer.

FIG. 2 shows a mass spectrogram of a hydrogenation product of a trimer.

FIG. 3 shows a ¹H-NMR spectrogram of a hydrogenation product of atrimer.

FIG. 4 shows a ¹³C-NMR spectrogram of a hydrogenation product of atrimer.

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

The embodiments of the present invention will be described in thefollowing.

The bicyclo[2.2.1]heptane derivative of the present invention isrepresented by the above general formula (1). Examples of the derivativeinclude3-methyl-2-[(3-methylbicyclo[2.2.1]hept-2-yl)methyl]-2-[(2,3-dimethylbicyclo[2.2.1]hept-2-yl)methyl]bicyclo[2.2.1]heptane,2-[(bicyclo-[2.2.1]hept-2-yl)methyl]-2-[(2-methylbicyclo[2.2.1]hept-2-yl)methyl]bicyclo-[2.2.1]heptaneand2-[(bicyclo[2.2.1]hept-2-yl)ethyl]-2-[(2-ethylbicyclo-[2.2.1]hept-2-yl)ethyl]bicyclo[2.2.1]heptane.From the standpoint of the effect exhibited by the compound,3-methyl-2-[(3-methylbicyclo[2.2.1]-hept-2-yl)methyl]-2-[(2,3-dimethylbicyclo[2.2.1]hept-2-yl)methyl]bicyclo-[2.2.1]heptaneis preferable. The chemical structure of this compound is expressed bythe following formula (2).

As the preferable process for producing the bicyclo[2.2.1]heptanederivative of the present invention, a material olefin can betrimerized, hydrogenated and distilled, successively.

Examples of the material olefin include bicyclo[2.2.1]heptanes havingmethyl group and methylene group, bicyclo[2.2.1]heptanes havingmethylene group, bicyclo[2.2.1]heptanes having ethylidene group,bicyclo[2.2.1]hept-2-enes having methyl group andbicyclo[2.2.1]-hept-2-enes having ethyl group. From the standpoint ofthe effect exhibited by the formed compound,2,3-dimethylbicyclo[2.2.1]hept-2-ene and3-methyl-2-methylenebicyclo[2.2.1]heptane are preferable.

The above trimerization includes trimerization of an olefin of a singletype and cotrimerization of a plurality of olefins of different types.

The above trimerization is conducted, in general, in the presence of acatalyst and, where necessary, with the addition of a solvent.

As the catalyst used for the trimerization, in general, an acidiccatalyst is used. Examples of the catalyst include solid acids such aszeolite, active clay, montmorillonite and ion exchange resins; mineralacids such as hydrofluoric acid and polyphosphoric acid; organic acidssuch as triflic acid; Lewis acids such as aluminum chloride, titaniumtetrachloride, iron trichloride, tin tetrachloride, boron trifluoride,complexes of boron trifluoride, boron tribromide, aluminum bromide,gallium chloride and gallium bromide; and organoaluminum compounds suchas triethylaluminum, diethylaluminum chloride and ethylaluminumdichloride. Since it is preferable that the trimerization is conductedat low temperatures, polyphosphoric acid, boron trifluoride, complexesof boron trifluoride, tin tetrachloride, titanium tetrachloride andaluminum chloride are preferable.

The amount of the catalyst is not particularly limited. In general, theamount of the catalyst is selected in the range of 0.1 to 100% by massbased on the amount of the material olefin.

For the trimerization, a solvent is not always necessary. A solvent maybe used from the standpoint of handling of the material olefin and thecatalyst in the reaction and the adjustment of the procedures of theprocess. Examples of the solvent include saturated hydrocarbons such asvarious types of pentane, various types of hexane, various types ofoctane, various types of nonane and various types of decane; alicyclichydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane anddecaline; ether compounds such as diethyl ether and tetrahydrofuran;compounds having halogens such as methylene chloride and dichloroethane;and nitro compounds such as nitromethane and nitrobenzene.

The trimerization is conducted in the presence of the catalyst describedabove. The temperature of the trimerization is, in general, 200° C. orlower and preferably 100° C. or lower so that the isomerization issuppressed. When the economy is also considered, it is preferable thatthe temperature is −70° C. or higher and more preferably −30° C. orhigher.

The conditions of the reaction can be suitably set in accordance withthe types of the catalyst, additives and the like. The pressure of thereaction is, in general, the atmospheric pressure, and the time is, ingeneral, in the range of 0.5 to 10 hours.

The trimer of the material olefin obtained as described above ishydrogenated, and the hydrogenation product of the trimer, i.e., theobject compound, is obtained.

The hydrogenation is, in general, conducted in the presence of acatalyst. Examples of the catalyst include hydrogenation catalysts suchas nickel, ruthenium, palladium, platinum, rhodium and iridium supportedon supports such as diatomaceous earth, silica-alumina and activecarbon; and Raney nickel. Among these catalysts, supported nickelcatalysts such as nickel/diatomaceous earth and nickel/silica-aluminaare preferable. The amount of the catalyst is, in general, in the rangeof 0.1 to 100% by mass based on the amount of the trimerization productdescribed above.

The hydrogenation can be conducted in the absence or in the presence ofsolvents similarly to the trimerization. Examples of the solvent includesaturated hydrocarbons such as various types of pentane, various typesof hexane, various types of octane, various types of nonane and varioustypes of decane; and alicyclic hydrocarbons such as cyclopentane,cyclohexane, methylcyclohexane and decaline.

The temperature of the hydrogenation is, in general, in the range of 100to 300° C. and preferably in the range of 160 to 280° C. When thetemperature is lower than 100° C., the hydrogenation does not proceedsufficiently, occasionally. When the temperature exceeds 300° C., theyield decreases due to decomposition. The pressure of the reaction is,in general, in the range of the atmospheric pressure to 20 MPa·G andpreferably in the range of the atmospheric pressure to 10 MPa·G. Thetime of the reaction is, in general, in the range of 1 to 10 hours.

The formed hydrogenation product can be purified by distillation.

The present invention will be described more specifically with referenceto examples in the following. However, the present invention is notlimited to the examples.

EXAMPLE 1

Into a 2 liter autoclave made of stainless steel, 561 g (8 moles) ofcrotonaldehyde and 352 g (2.67 moles) of dicyclopentadiene were placed,and the reaction was allowed to proceed under stirring at 170° C. for 3hours. After the obtained reaction solution was cooled to the roomtemperature, 18 g of a Raney nickel catalyst (manufactured by KAWAKENFINE CHEMICALS Co., Ltd.; M-300T) was added, and the hydrogenation wasconducted under a hydrogen pressure of 0.88 MPa·G at a temperature of150° C. for 4 hours. After the reaction mixture was cooled and thecatalyst residue was removed by filtration, the filtrate was distilledunder a reduced pressure, and 565 g of a fraction of 105° C./2.67 kPawas obtained. As the result of the analysis of the obtained fractionbased on the mass spectrum and the nuclear magnetic resonance spectra,the fraction was identified to be2-hydroxymethyl-3-methylbicyclo[2.2.1]-heptane.

Into a flow type atmospheric reaction tube made of quartz and having adiameter of 20 mm and a length of 500 mm, 20 g of γ-alumina(manufactured by NIKKI CHEMICAL Co., Ltd.; N612) was placed. Thedehydration was conducted at a temperature of 285° C. and a weighthourly space velocity (WHSV) of 1.1 hr⁻¹, and 490 g of a dehydrationproduct of 2-hydroxymethyl-3-methylcyclo[2.2.1]heptane was obtained. Theproduct contained 2-methylene-3-methylbicyclo[2.2.1]heptane and2,3-dimethylbicyclo[2.2.1]hept-2-ene.

Preparation of a Hydrogenation Product of a Trimer

Into a 500 ml four-necked flask, 4.0 g of boron trifluoride diethyletherate and 200 g of the olefin compound obtained above were placed.The resultant mixture was stirred by a mechanical stirrer at 20° C. for6 hours, and the oligomerization was conducted. The obtained reactionmixture was washed with a dilute aqueous solution of sodium hydroxideand a saturated aqueous solution of sodium chloride. Into a 1 literautoclave, 6 g of a nickel/diatomaceous earth catalyst for hydrogenation(manufactured by NIKKI CHEMICAL Co., Ltd.; N-113) was added, and thehydrogenation of the reaction mixture obtained above was conducted undera hydrogen pressure of 2.94 MPa·G at a temperature of 250° C. for a timeof 5 hours. After the reaction was completed, the catalyst was removedby filtration. The filtrate was distilled under a reduced pressure, and30 g of a hydrogenation product of the trimer was obtained as a fractionhaving a boiling point of 240 to 250° C./1.33 kPa. In accordance withthe mass chromatography, the mass spectrography and the nuclear magneticresonance spectrography, the hydrogenation product of the trimer wasidentified to be3-methyl-2-[(3-methylbicyclo[2.2.1]-hept-2-yl)methyl]-2-[(2,3-dimethylbicyclo[2.2.1]hept-2-yl)methyl]bicyclo[2.2.1]heptane.The mass chromatogram of this compound is shown in FIG. 1, the massspectrogram is shown in FIG. 2, the ¹H-NMR spectrogram is shown in FIG.3, and the ¹³C-NMR spectrogram is shown in FIG. 4. The properties areshown in Table 1.

COMPARATIVE EXAMPLE 1

The properties of a polybutene (manufactured by IDEMITSU PETROCHEMICALCo., Ltd.; 100H) are shown in Table 1.

COMPARATIVE EXAMPLE 2

The properties of an ethylene-propylene oligomer (manufactured by MITSUICHEMICALS Co., Ltd.; LUCANT HC600) are shown in Table 1.

COMPARATIVE EXAMPLE 3

The properties of a poly-α-olefin (manufactured by AMOCO Company;DURASYN 180) are shown in Table 1.

TABLE 1 Comparative Comparative Comparative Example 1 Example 1 Example2 Example 3 Kinematic 11,000 6,800 9,850 1,250 viscosity (@ 40° C.)mm²/s Kinematic 51 210 600 100 viscosity (@ 100° C.) mm²/s Viscosityindex −500 124 240 168 Aniline point ° C. 83 160 170 155

INDUSTRIAL APPLICABILITY

The bicyclo[2.2.1]heptane derivative of the present invention exhibitsexcellent compatibility with various organic compounds, has a smallviscosity index and is used as the high viscosity hydrocarbon basematerial used for tackfiers for adhesives and process oils for rubberand resins.

1. A composition comprising at least 81% of a bicyclo[2.2.1]heptanecompound represented by the following general formula (1):

wherein R¹ and R² each represent hydrogen atom or methyl group, and R³represents methyl group or ethyl group.
 2. The composition according toclaim 1, which comprises a compound of formula (I) that is3-methyl-2-[(3-methylbicyclo[2.2.1]hept-2-yl)methyl]-2-[(2,3-dimethylbicyclo[2.2.1]-hept-2-yl)methyl]bicyclo[2.2.1]heptane.3. The composition according to claim 1, which comprises a compound offormula (I), which has a boiling point ranging from 240 to 250° C. at1.33 kPa.
 4. The composition of claim 1 which that comprises a compoundof formula (I), wherein R¹ is hydrogen.
 5. The composition of claim 1that comprises a compound of formula (I), wherein R¹ is methyl.
 6. Thecomposition of claim 1 that comprises a compound of formula (I), whereinR² is hydrogen.
 7. The composition of claim 1 that comprises a compoundof formula (I), wherein R² is methyl.
 8. The composition of claim 1 thatcomprises a compound of formula (I), wherein R³ is methyl.
 9. Thecomposition of claim 1 that comprises a compound of formula (I), whereinR³ is ethyl.
 10. A tackifier composition comprising the composition ofclaim
 1. 11. An adhesive composition comprising the composition ofclaim
 1. 12. A process oil composition comprising the composition ofclaim
 1. 13. A method for making a tackifier comprising incorporatingthe composition of claim 1 into a tackifier.
 14. A method for making aprocess oil for rubber or resin comprising incorporating the compositionof claim 1 into said process oil.
 15. A process for preparing acomposition containing at least 81% of a bicyclo[2.2.1]heptane compoundwhich compound has a boiling point ranging from 240 to 250° C. at 1.33kPa, comprising: (a) preparing a trimer by trimerization of a materialolefin selected from the group consisting of bicyclo[2.2.1]heptaneshaving a methyl group and a methylene group, bicyclo[2.2.1]heptaneshaving a methylene group, bicyclo[2.2.1]heptanes having an ethylidenegroup, bicyclo[2.2.1]hept-2-enes having methyl group, andbicyclo[2.2.1]hept-2-enes having an ethyl group; (b) hydrogenating thetrimer; and (c) distilling the hydrogenation product of the trimer. 16.The process according to claim 15, wherein the material olefin is adehydration product of 2-hydroxymethy-3-methylcyclo[2.2.1]heptane.